CS219666B1 - Mixed disfunctional catalyzer for catalytic hydroconversion of the hydrocarbons and method of making the same - Google Patents

Abstract

The subject of the invention is a catalyst suitable for the invention hydrocarbon hydrocarbon conversion and process production. The catalyst contains two aluminosilicate component and metal component, One Aluminosilicate the component is a synthetic aluminosilicate containing bound metals, the second component is selected from a group comprising rhodium aluminosilicates type and pole. The metal component is selected from metals Groups 6 to 8 of the Periodic System. Method of production the catalyst comprises homogenizing the individual components and heat treatment provided conditions. The catalyst can be used in catalytic form hydroconversion of hydrocarbons or mixtures hydrocarbons such as hydrocracking, disproportionation, hydroisomerization, hydrodearomatization disalkylation, transalkylation and the like.

Description

The present invention relates to a new type of mixed difunctional catalysts effective for catalytic hydroconversion of hydrocarbons or mixtures of hydrocarbons and a process for their preparation.

Hydroconversion is understood to mean the conversion of hydrocarbons or a mixture of hydrocarbons taking place in the presence of hydrogen or hydrogen-containing gas. Hydroconversion of hydrocarbons contemplated by the invention relates to hydrocracking, disproportionation, hydrodearomatization, hydroisomerization, desalkylation, catalytic reforming, transalkylation and similar processes taking place on difunctional catalysts.

More specifically, catalytic hydroconversion plants of hydrocarbons or mixtures of hydrocarbons are understood to mean the hydrotreating of petroleum distillates or hydrocarbon distillates obtained from coal processing; hydroisomerizing alkanes, cycloalkanes, alkylated aromatic hydrocarbons, alkenes, and / or mixtures thereof;

hydrogenated dearomatization of motor and jet fuels; disproportionation of alkenes, cycloalkenes and alkyl-substituted aromatic hydrocarbons; de-alkylation of alkylaromatic hydrocarbons; Transalkylation of aromatic hydrocarbon mixtures with different numbers of alkyl substituents and catalytic reforming of hydrocarbon distillates boiling in the gasoline distillation range * The hydrocarbons or hydrocarbon mixtures considered may, but need not, contain sulfur and / or nitrogen compounds as accompanying substances.

In many chemical processes, natural or synthetic aluminosilicates which are either amorphous or crystalline are used as catalysts. These aluminosilicates together with the metals 6 to 6

8. Periodic groups (e.g. Mo, Re, Pt, Pd, Ni, Co, Ir, etc.) in the form of difunctional catalysts are widely used in hydroprocesses such as hydrocracking, hydroisomerization, disproportionation, transalkylation and the like.

Thus, the difunctional catalysts comprise two active components; aluminosilicate (acid component) and metal, respectively. its compound (hydrogenation / dehydrogenation component). Difunctional catalysts containing crystalline zeolite as the acid component are in most cases more active and selective than catalysts containing amorphous aluminosilicates. More attractive difunctional catalysts include those containing the H-form of synthetic mordenite.

The invention relates to a new type of difunctional catalysts which are more active and selective than difunctional catalysts containing the H-form of synthetic mordenite as an acid component. The described difunctional catalysts according to the invention can be termed mixed difunctional catalysts in terms of the phase composition of the acid component of these catalysts.

The mixed difunctional catalysts of the present invention suitable for the catalytic hydroconversion of hydrocarbons or mixtures of hydrocarbons are prepared by mixing together the individual aluminosilicate components A and B, wherein component A is a synthetic layered aluminosilicate having the empirical formula m SiO ₂ : n Al ₂ O ₃ : with DM: t H ₂ O in which is

SiO ₂ silica

Al ₂ O ₃ alumina

QO metal oxide or oxides selected from the group consisting of copper, beryllium, magnesium, zinc, nickel, cobalt,

D equivalent of anions selected from the group consisting of hydroxyl anion, fluoride anion, chloride anion, oxygen anion,

M equivalent of exchangeable cation or cations selected from the group consisting of hydrogen, ammonium, alkali metal, alkaline earth metal,

HO is water, wherein in molar ratios m has a value from 2.01 to 3.97 n has a value from 0.02 to 2.96 p has a value from 0.03 to 3.50 s has a value from 0.03 to 1, 00 t has a value from 3,50 to 5,10 at 60% relative humidity,

Component B for the purposes of the invention is a material selected from the group consisting of alumina, silica and / or crystalline aluminosilicates such as type X zeolites, type Y zeolites, halloyzite, natural or synthetic montmorillonite, kaolinite, natural mordehite, natural or synthetic clinoptilolite , their mixtures natural or artificial or their natural mixed structures.

The preparation of the catalysts according to the invention comprises homogenizing the mixture of said components A and B dry (e.g. in a ball mill) and / or wet, shaping the homogenized mixture in order to obtain the catalyst in the desired dimensions and shapes such as grains, exudates, tablets and others. The catalysts thus prepared according to the invention are further dried at 80 ° C-150 ° C and calcined at a temperature of 150 ° C-700 ° C.

In order to obtain difunctional catalysts, hydrogenation metals of the 6-8th period, such as platinum, palladium, nickel, cobalt, iridium, rhenium, molybdenum and the like, need to be introduced into these components prior to mixing the aluminosilicate components A and B. and / or mixtures thereof with known methods such as e.g. impregnation or ion exchange. Said hydrogenation metals may also be introduced after mixing of components A and B, i. j. to a mixture of components A and B. Both processes or a combination thereof can produce catalysts having high activity and selectivity.

The final step in the preparation of the catalysts of the present invention is to reduce the calcined catalyst in a hydrogen or hydrogen-containing gas stream to bring the metals of the 8th periodic group to an atomic state, which is usually done directly in the reactor.

The mixed difunctional catalysts of the invention comprise aluminosilicate components A and B, the content of component A in the catalyst mixture of components A and B being from 10% to 95% by weight. and a metal or a mixture of metals of the 7th and 8th groups in an amount of from 0.01% to 6.5% by weight. and in the presence of metals of the 6th period, from 0.5 to 25 wt. to the total catalyst mass.

The following examples illustrate the method of preparation, advantages and practical use of the catalysts of the invention, but without limiting the scope of the invention in any way.

Example 1.

Synthetic Y-zeolite with a molar ratio of SiO2: ALO = 5.1 in ammonium form was mixed with component A containing zinc and wet homogenized for 8 hours. A solution of [Pd (NH ₃ ) ₄ ] Cl _{2 was} then slowly added to the mixture so that the resulting material contained 0.8% by weight at 110 ° C after drying. palladium, 60% Y-zeolite and 39.2% of component A. The dried catalyst, denoted A, was further calcined at 450 ° C and, after loading into the reactor, was activated in a H ₂ stream at 420 ° C.

Example 2.

Natural clinoptilotite was activated in 0.2 N HCl solution for 3 hours. After subsequent ion exchanges in the ammonium salt solution, clinonitrile ammonium form was prepared and calcined at 450 ° C. A homogeneous mixture was prepared from the treated clinoptilolite, nickel-beryllium-bound component A and γ-alumina, which was impregnated with H ₂ PtCl _{6 solution} . The obtained catalyst, designated B, after drying at 120 ° C contained;

39.5% clinoptilolite, 30% component A, 30% wt. γ-alumina and 0.5% platinum. and

Example 3.

100 g of natural halloyzite, for which ionic | with an ammonium acetate solution, alkali metal cations were removed and wet-homogenized. vala with 11.0 g of component A with structurally bound nickel for 5 hours. K obtained homogeneous; [Pd (NH ₃ ) ₄ ] Cl ₂ 'solution was added such that the catalyst C obtained after drying at 120 ° C and calcining at 450 ° C contained 0.48 wt. | palladium. -,

Example 4 _.;

Natural mordenite was treated with acidic activation followed by an ionic NH ₄ NO _{3 solution} . The obtained ammonium form was homogenized wet with component A containing nickel for 6 hours, after which a solution of H ₂ PtCl ₆ was added to the prepared homogeneous mixture so that the platinum content in the dried catalyst D was 0.6% by weight.

The dried catalyst was calcined at 540 ° C for 2 hours and then activated in the reactor at 480 ° C under hydrogen flow.

Example 5.

The catalytic activity of the difunctional catalysts of the present invention in the hydrogenation cracking process was monitored on a conventional type flow microaparatrix at a pressure of 0.25 MPa on a n-hexane hydrocracking model reaction. Synthetic mordenite in H-form with a molar ratio of 17.6 SiO ₂ / Al ₂ O ₃ containing 0.8 wt. platinum. The spatial volume velocity of the injected n-hexane was 1.0 h ¹ .

The reaction products were analyzed by gas chromatography. As the results show experimentally (Table 1), the catalysts of the invention are characterized by high activity, and the n-hexane conversion of the catalysts according to the invention is achieved at a lower temperature than on the Pt / H-mordenite catalyst.

Example 6.

The catalytic activity of the catalysts according to the invention in the process of hydroisomerization of n-hexane is investigated It had a hydrogen atmosphere at a pressure of 0.25 MPa, a bulk material velocity of 1.0 h ^-1 and a temperature range of 200-330 ° C. An industrial isomerization catalyst: Pt / H-mordenite (0.4 wt% platinum) was used as a comparative catalyst. ^Iso: Merize was analyzed by gas chromate Photographic credits. As shown experimentally (Table 2), the catalysts of the invention are characterized by high activity and selectivity, mainly in view of the production of dimethylbutanes, which, by virtue of their high octane number, are the most valuable hydrocarbons in the isomerisate.

The selective hydroisomerization activity and selectivity of the catalysts of the invention best reflects the selective conversion at dime parameter; tylbutanes, which is 2.9 times the weight of the present industrial isomerization catalyst, as well as the selective conversion to iso-C ₅ / C ₆ parameter, which is 2.3 times the weight of the catalysts of the invention compared to the comparative industrial catalyst (see Table 2).

Table 1.

catalyst According to the invention comparative Pt / H-mordenite catalyst A catalyst B Temperature ° C Conversion of n-hexane (wt.%) 220 23.88 21.63 ¹ 14.95 240 41.25 34.84 29.67 260 58.29 57.68 45.91 280 . 69.76 76.51 63.77 300 83,69 85,89 79,27 320 91.75 89.71 86,71

Table 2.

catalyst According to the invention Comparative industrial Pt / H-mordenite catalysis. C catalysis. D Temperature ° C 260 260 300 Product composition% wt. i-pentane 8.31 0.45 5.65 n-pentane 6.13 0.37 1.42 2,2-dimethylbutane 9.40 7.26 3.73 2,3-dimethylbutane 4.04 6.72 4.74 2-methylpentane 25.83 34.97 21.02 3-methylpentane 15.76 23.16 13.45 n-hexane 15.98 20.20 20.73 methylcyclopentane 0.56 1.35 0.62 benzene - - 0.07 cyclohexane 0.15 0.34 0.14 dimethylbutanes (DMB) selective. conversion to 13.44 13.98 8.47 DMB selective. conversion to 45.07 55.08 17.24 IZOCg / Cfi ²⁾ 1.78 2.88 0.98 Yield C ₅ ⁺ 86.16 94,82 71.59

⁰ Selective conversion to DMB - __% DMB__% (Ci + C2 + C3 + C4 + nCu) ²⁾ Selective conversion to isoC ₅ / C ₆ = __% (iC ₅ + iC ₆ + cycloC ₆ ) _% (C ₍ + C-2 (C3 + C4 + nC ₅ + nCg)

Claims (2)

5 Table 2. Catalyst According to the Invention Comparison of industrial Pt / H-mordenite catalysis. C catalysis. D Temperature ° C 260 260 300 Product composition% wt-pentane 8.31 0.45 5.65 n-pentane 6.13 0.37 1.42 2.2-dimethylbutane 9.40 7.26 3.73 2,3-dimethylbutane 4.04 6.72 4.74 2-methylpentane 25.83 34.97 21.02 3-methylpentane 15.76 23.16 13.45 n-hexane 15.98 20.20 20.73 methylcyclopentane 0.56 1.35 0.62 benzene - - 0.07 cyclohexane 0.15 0.34 0.14 dimethylbutanes (DMB) selective. conversion to 13.44 13.98 8.47 DMB selective. conversion to 45.07 55.08 17.24 IZOCg / Cfi 2) 1.78 2.88 0.98 Yield C5 + 86.16 94.82 71.59 0 Selective conversion to DMB - __% DMB__% (C1-4) C2 4- C3 + C4 + nC1) 2) Selective conversion to isoC5 / C6 = _ (% C5-4C6-4cycloC6)% (C (4 * C-2 4 "C3-4C4 * nC5 4") nCg) SUBJECT OF THE INVENTION A mixed difunctional catalyst for catalytic hydroconversion of hydrocarbons or mixtures of hydrocarbons such as hydrogenation cracking, hydroisomerization, dealkylation, hydrodearomatization, catalytic reforming, transalkylation, dispersion, characterized in that it contains aluminum-silicate components A, B and metal component, wherein component A is a synthetic layered aluminate-silicate with the formula empirical formula m SiO 2: n A 2 O 3: p QO: with DM: t H 2 O in which SiO 2 is silicon dioxide * A12O3 alumina QO metal oxide or oxides selected from copper, beryllium magnesium, zinc, nickel, cobalt, 219666 D equivalent of anions selected from the group consisting of hydroxyl anion, fluoride anion, chloride anion, oxygen anion, M equivalent of exchangeable cation or cations selected from hydrogen, ammonium, alkali, alkaline earth, óny Water, with molar ratios having a value from 2.01 to 3.97 n having a value from 0.02 to 2.96 p having a value from 0.03 to 3.50 s having a value from 0.03 to 1.00 t having a value from 3.50 to 5.10 at 60% relative humidity, component B comprises substances from the group such as alumina, silica gel, crystalline aluminosilicates, zeolites X, zeolites Y, halloyzite, natural montmorillonite, synthetic montmorillonite, kaolinite, natural mordenite, clinoptilolite wherein the content of component A in the catalyst is from 10% to 95% by weight, the content of component B being from 5% to 90% by weight. and the metallic particulate in the atomic state or in the form of its oxide or sulphide is selected from the groups 6-8 of the preferred group including platinum, palladium, nickel, cobalt, iridium, rhenium, molybdenum, the metal component of the catalyst being metal 7 and 8. a periodic group of from 0.01% to 6.5% by weight. and in the case of the 6th periodic group, from 0.5 to 25% by weight. 2. A method for producing a mixed difunctional catalytic hydrocarbon conversion catalyst according to claim 1, characterized in that it comprises homogenizing the aluminosilicate constituents A and B in the dry or wet form, further forming the homogenized mixture of components A and B in the particle, drying the particles. at a temperature of from 70 ° C to 150 ° C, calcination of the dried particles at a temperature of from 150 ° C to 700 ° C, preferably from 350 ° C to 550 ° C, and heat treatment in the presence of hydrogen or hydrogen-containing gas at a temperature of; 200 ° C to 650 ° C, preferably from 320 ° C to 480 ° C, wherein the metal component is introduced into the individual aluminosilicate builders A and B prior to mixing or into the mixture of components A and B during or after homogenization, but prior to thermal treatment in the presence of hydrogen or hydrogen-containing hydrogen.